Postdiagenetic Changes in Kerogen Properties and Type by Bacterial Oxidation and Dehydrogenation

A significant part of organic carbon found on the earth is deposited as fossil organic matter in the lithosphere. The most important reservoir of carbon is shale rocks enriched with organic matter in the form of kerogen created during diagenesis. The purpose of this study was to analyze whether the bacterial communities currently inhabiting the shale rocks have had any impact on the properties and type of kerogen. We used the shale rock located on the Fore-Sudetic Monocline, which is characterized by oil-prone kerogen type II. We were able to show that shale rock inhabited by bacterial communities are characterized by oxidized and dehydrated kerogen type III (gas-prone) and type IV (nonproductive, residual, and hydrogen-free). Bacterial communities inhabiting shale rock were dominated by heterotrophs of the Proteobacteria, Firmicutes, and Actinobacteria phyla. Additionally, we detected a number of protein sequences in the metaproteomes of bacterial communities matched with enzymes involved in the oxidative metabolism of aliphatic and aromatic hydrocarbons, which may potentially contribute to the postdiagenetic oxidation and dehydrogenation of kerogen. The kerogen transformation contributes to the mobilization of fossil carbon in the form of extractable bitumen dominated by oxidized organic compounds.     

X射线荧光光谱法直接测定油页岩中微量元素

本文提出用微晶纤维素与GSD等国家一级系列标样按不同比例混合制备标准样品。油页岩样品不经前处理,直接粉末法压片,经验系数法校正元素间效应,直接测定油页岩中V、Co、Ni、Cr、Cu、Zn、Sr、Ba和Rb等元素的X射线荧光光谱法。样品分析结果与ICP-AES法分析结果基本一致,本法具有简单、准确、实用的特点。     

油页岩固定床热解反应器中内构件强化作用

在内构件(传热板和中心集气管)外热式固定床反应器中研究了油页岩热解产物生成特性,并与无内构件的相同常规固定床反应器内的油页岩热解行为对比,考察了两反应器中油页岩升温特性、热解产物分布、页岩油品质以及气体产物组成的变化规律.结果表明,内置传热板和中心集气管显著强化了反应器内的传热,相对于无内构件常规固定床反应器,料层升温速率提高了约2倍.对于依兰油页岩,其热解页岩油产率明显提高,最高达11.1 wt%(干燥基),明显高于无构件常规固定床反应器获得的页岩油产率.随着外加热炉温度的升高,内构件固定床反应器的页岩油产率逐渐增加,而无内构件常规固定床反应器的页岩油产率则明显降低.当外加热炉温度为1000℃时,前者页岩油产率是后者的2.3倍,并且内构件固定床反应器的热解水产率较低.两反应器中热解气产物组成相近,其H2与CH4之和占气体总量的70 vol%左右,热值为4406~5400 kcal/Nm3.     

页岩气储层压裂数值模拟技术研究进展

页岩气储层水力压裂数值模拟既要考虑页岩储层岩石的特性,又要兼顾水平井分段压裂施工工艺,是一个非常棘手的力学难题.本文简述了页岩气储层岩石具有的地质力学特征和页岩气储层开发常用的水平井分段压裂技术;详述了扩展有限元、边界元、离散元在水力压裂裂缝模拟上的应用现状,指出了它们在处理裂缝问题的局限性和优越性,总结出边界元三维位移不连续法是模拟多裂缝扩展的有效方法.     

桦甸油页岩热解特性的研究

在热分析仪上进行了桦甸油页岩的热解特性研究,升温速率分别为10℃/min、20℃/min、30℃/min和40℃/min,终温为900℃。实验表明油页岩的热解是分两步进行的。在低温段主要是油页岩中可挥发性的气体溢出引起热解失重;高温段则主要是一些有机质、固定碳的热解过程。低温段的热解是主要的,它基本上热解掉了油页岩重量的15％－27％左右,油页岩挥发分含量很高且具有集中析出的特性,在400℃－530℃区间内可挥发物质迅速热解守比,其在高温段的热解产率很小,只有总重量的10％左右。随着升温速率的增加低温段的高温段热解的区分更加明显,且使油页岩的热解产率提高。文中给出了不同升温速率下的桦甸油页岩热解特性数据和化学反应动力学参数。     

页岩气和致密砂岩气藏微裂缝气体传输特性

页岩气和致密砂岩气藏发育微裂缝,其开度多在纳米级和微米级尺度且变化大,因此微裂缝气体传输机理异常复杂.本文基于滑脱流动和努森扩散模型,分别以分子之间碰撞频率和分子与壁面碰撞频率占总碰撞频率的比值作为滑脱流动和努森扩散的权重系数,耦合这两种传输机理,建立了微裂缝气体传输模型. 该模型考虑微裂缝形状和尺度对气体传输的影响. 模型可靠性用分子模拟数据验证.结果表明:(1)模型能够合理描述微裂缝中所有气体传输机理,包括连续流动,滑脱流动和过渡流动;(2)模型能够描述不同开发阶段,微裂缝中各气体传输机理对传输贡献的逐渐变化过程;(3)微裂缝形状和尺度影响气体传输,相同开度且宽度越大的微裂缝,气体传输能力越强,且在高压和微裂缝大开度的情况下表现更明显.      

钻井完井液浸泡弱化页岩脆性机制

页岩脆性是页岩地层钻井、水力压裂设计的关键参数之一,目前针对钻井过程中工作液浸泡对页岩脆性的影响还未引起关注.通过开展钻井完井液浸泡前后页岩三轴力学实验,利用脆性评价模型分析了页岩脆性变化特征.结果表明,延长组页岩脆性强于龙马溪组页岩;油基和水基钻井完井液浸泡均能导致页岩脆性降低,且油基钻井完井液浸泡后的页岩脆性降低幅度更大;龙马溪组页岩浸泡后脆性减弱幅度较延长组页岩大.页岩脆性弱化机制包括:(1)由层理面胶结强度不同引起的脆性强弱差异;(2)由毛管自吸作用导致的高孔压、高应力强度因子、低临界断裂韧性;(3)由碱液侵蚀导致的页岩溶蚀孔形成及矿物颗粒碎裂;(4)由黏土矿物水化膨胀产生的膨胀应力;(5)由钻井完井液滤液润滑导致的页岩破裂面摩擦系数降低.延长组页岩层理面强度较龙马溪组页岩低,导致延长组页岩脆性强于龙马溪组页岩.其次,和水基钻井完井液相比,油基钻井完井液具有更大的自吸量、更高的pH值、更强的润滑性,因此,油基钻井完井液浸泡降低页岩脆性幅度更大.另外,由于龙马溪组页岩具有更小的润湿角、更强的毛管自吸和碱液侵蚀作用,相同浸泡条件下,龙马溪组页岩脆性降低幅度更大.本研究可为页岩地层钻井液性能优化、井壁稳定控制、水力压裂设计等提供理论指导.      

Evaluation of Oil Yield of Oil Shale by Infrared Spectrometry Coupled with Ultrasound-assisted Extraction

The oil yield of oil shale was evaluated by Fourier transform infrared(FTIR) spectrometry coupled with ultrasound-assisted extraction. The extraction conditions, including the amount of sample, extraction time and extraction temperature, were examined and optimized. Twenty-four oil shale samples were collected and divided into calibration set and prediction set randomly with a ratio of 2:1. The oil yields of all the samples were determined by the routine method(low-temperature retorting) for reference. The linear regression(LR) equations of oil yield vs. the total area of the spectrum peaks in a wavenumber range of 3100-2800 cm^-1 as well as the sum of absorbance of three absorption peaks(2855, 2927 and 2955 cm^-1), and the multiple linear regression(MLR) model of oil yield vs. the absorbances of the three absorption peaks were constructed with the samples in calibration set and applied to the evaluation of the oil yields of the samples in prediction set, respectively. The results show that the MLR model provides more accurate predictions than the other LR two equations. The determination coefficient(R_p²), the root-mean-square error of prediction(RMSEP) and the residual prediction deviation(RPD) of the MLR model are 0.9616, 0.6458 and 3.6, respectively. The present method is a rapid and effective alternative to the routine low-temperature retorting method.     

抚顺页岩油的高分辨核磁共振研究

用高分辨液体核磁共振氢谱、碳谱、二维碳氢相关谱和DEPT谱(无畸变极化转移增强法)对我国抚顺页岩油的不同组分进行了详细研究,得出了一些结构信息和变化规律。     

The role of MgO in the binding of SO<Subscript>2 </Subscript>by lime-containing materials

Summary The results of investigation of MgO participation in the binding of SO₂ with lime-containing materials as sorbents are presented. Experiments of SO₂ binding into solid phase using model samples of reactive grade MgO and CaO varying the mole ratio of MgO/CaO from 9:1 to 1:9 were carried out. Besides, dolomite and limestone samples with different MgO/CaO mole ratio (from 1.24 to 0.13) and samples of ashes formed at combustion of Estonian oil shale (containing 35-40% of carbonates) and its semicoke were studied Initial samples, intermediate and final products were subjected to chemical, IR-spectroscopy, X-ray and BET specific surface area analyses. The results of the present study confirmed the active participation of MgO in the binding of SO₂ into the solid phase. In addition to CaSO₄ the formation of Ca,Mg-double sulphate CaMg₃(SO₄)₄ and -MgSO₄ was observed. The presence of CaMg₃(SO₄)₄ was fixed in a large temperature range 400-900°C and that of -MgSO₄ in between 500-700°C. The optimum temperature range for formation and durability of CaMg₃(SO₄)₄ was 700-800°C.